Petroleum lubricants stabilized with bactericides



United States Patent 3,183,189 PETROLEUM LUBRICANTS STABILIZED WITHBACTERICIDES Edward B. Hodge, Terre Haute, Ind., assignor to CommercialSolvents Corporation, New York, N.Y., a corporation of Maryland NoDrawing. Filed Mar. 20, 1961, Ser. No. 96,695

16 Claims. (Cl. 252-495) My invention relates to a stabilized petroleumlubricant and more particularly to a process for the production ofstabilized petroleum lubricants containing as the active stabilizingagent nitroamines having the structural formula:

where R is selected from the group consisting of lower alkyl andhydrogen; where R; is a member selected from v stabilization of variouspetroleum products such as cutting oils, hydraulic fluids,'etc.,'against breakdown by bacteria which metabolize the hydrocarbonswith the concurrent formation of deleterious metabolites.

Many compounds have been used as stabilization agents in lubricants, butvery few have been found to be commercially successful due to the factthat the compounds are unstable, or are not active against a widevariety of microorganisms.

Among the nitroamines having the above structural formula are includedN-(Z-nitroisbbutyl)diisopropylamine, N- Z-nitropropyl morpholine, N-2-nitropropyl) dibutylamine, N (2 nitropropyl)diisobutylamine,N-(Z-nitrobutyl)dimethylamine, N -(2-nitrobutyl) 2 -'ethylhexylamine,N-(2-nitrobutyl)-l-amino-2-propanol, N-(Z-nitrobutyl)morpholine, N (2nitrobutyl)piperidine, N (2- nitrobutyl)tetrahydrofurfurylamine, etc. Ihave found that in some instances I can obtain total inhibition ofbacterial growth in petroleum lubricants at concentrations as low as 100ppm. I prefer to include at least 1,000 p.p.m. in most petroleumformulations. However, I can employ amounts up to about 2% by weight ofthe active nitroamines when the latter is soluble to this extent in theparticular petroleum hydrocarbon composition.

I have found that my active ingredients are effective bacteriostatic'agents in petroleum containing lubricants such as cutting oils,penetrating oils, grinding lubricants, iron tinning lubricants, coreoils, hydraulic fluids, etc.

The following examples set out lubricating compositions in which myactive ingredients act as effective bacteriostatic agents. It is notintended that my invention be limited to the compositions, portions, orlubricants set out below; but rather I intend for all equivalents andvariations obvious to those skilled in the art to be included within thescope of this specification and the attached claims.

EXAMPLE I To test the use of my active ingredients in cutting oils, a 25:1 water-cutting oil emulsion was prepared. The cutting oil concentrateused was a proprietary-cutting oil containing no bacteria inhibitorssuch as that sold by Texaco Incorporated under the name of Soluble OilTexaco-C. To each of one-gallon containers was added 1 liter ofwater-cutting oil emulsion. Desired amounts of my nitroamines were addedto the cutting-oil emulsion in the first container. No inhibitor wasadded tothe other container which was used as a control. At thebeginning of the experiment, each unit was inoculated with 5 mls. of aheterogeneous bacterial culture which had grown for several years in awater-cutting oil emulsion. Aeration and mixing were obtained by usingan air lift to continually circulate the mixture. The test was continuedfor a period of six weeks and during the six- 1 week period, 5 mls. ofbacterial culture were added at periodic weekly intervals.

The following table sets out the results of the above tests and thenumber of days of bacterial irihibitionwhen the described concentrationof the desired nitroamines were incorporated into the cutting-oilemulsion.

\ EXAMPLE II The following is a water emulsifiable cutting oil which isadequately protected by 1,000 p.p.m. of my nitroamine inhibitors:

Percent by weight Light mineral oil 90 Oleic acid l0 EXAMPLE III Thefollowing is a stabilized steam cylinder oil which is adequatelyprotected by 1,000 p.p.m. of N-(2-nitrobutyl dimethylamine. r

Percent S.A.E. lubricating oil 90 Oleic'acid l0 EXAMPLE IV The followingis a core oil which is adequately protected by 1,000 p.p.rn. ofN-(2-nitrobutyl)morpholine.

Percent Crude tall oil 25 Fuel oil Tall oil ester (glycol or glycerol)40 EXAMPLE v The following is a cutting oil which is adequatelyprotected by 1,000 p.p.m. of N-(Z-nitrobutyl)piperidine.

Percent Tallow Paraffin wax 29 Beeswax 1.3 Oxalic acid 1.3 Potassiumcitrate 1.3 Urea 0.4

Patented May 11, I965 Now having described my invention, what I claimis:

l. A liquid petroleum composition consisting essentially of a liquidpetroleum lubricant hydrocarbon and a sufiicient amount ofN-(Z-nitroisobutyl)diisopropylamine to stabilize said hydrocarbonagainst metabolizing bacteria.

2. A liquid petroleum composition consisting essentially of a liquidpetroleum lubricant hydrocarbon and a suflicicnt amount ofN-(Z-nitropropyl)morpholine to stabilize said hydrocarbon againstmetabolizing bacteria.

3. A liquid petroleum composition consisting essentially of a liquidpetroleum lubricant hydrocarbon and a sufiicicnt amount ofN-(Z-nitropropyl)dibutylamine to stabilize said hydrocarbon againstmetabolizing bacteria.

4. A, liquid petroleum composition consisting essentially of a liquidpetroleum lubricant hydrocarbon and a sufficient amount ofN-(Z-nitropropyl)diisobutylamine to stabilize said hydrocarbon againstmetabolizing bacteria.

5. A liquid petroleum composition consisting essentially of a liquidpetroleum lubricant hydrocarbon and a sufficient amount ofN-(2-nitrobutyl)dimethylamine to stabilize said hydrocarbon againstmetabolizing bacteria.

6. A liquid petroleum composition consisting essen-.

tially of a liquid petroleum lubricant hydrocarbon and a sufiicientamount of N-(Z-nitrobutyl)-2-ethylhexylamine to stabilize saidhydrocarbon against metabolizing bacteria.

7. A liquid petroleum composition consisting essen-.

tially of a liquid petroleum lubricant hydrocarbon and a sufficientamount of N-(Z-nitrobtityl)-1-amino-2-propanol to stabilize saidhydrocarbon against metabolizing bacteria.

8. A liquid petroleum composition consisting essentially of a liquidpetroleum lubricant hydrocarbon and a suflicient amount ofN-(Z-nitrobutyl)morpholine to stabilize said hydrocarbon againstmetabolizing bacteria.

9. A liquid petroleum composition consisting essentially of aliquidpetroleum lubricant hydrocarbon anda sufiicient amount ofN-(2-nitrobutyl)piperidine to stabilize said hydrocarbon againstmetabolizing bacteria.

10. A liquid petroleum composition consisting essentially of a liquidpetroleum lubricant hydrocarbon and a sulficient amount ofN-(Z-nitrobutyl)tetrahydrofurfurylamine to stabilize said hydrocarbonagainst metabolizing bacteria.

11. An aqueous petroleum emulsion consisting essentially of an aqueouspetroleum lubricant hydrocarbon emulsion and a sufiicient amount of anitroamine to stabilize said hydrocarbon against metabolizing bacteria,said nitroamine having the structural formula:

where R is selected from the group consisting of lower alkyl andhydrogen; where R is a member selected from the group consisting of -N(Rmorpholino, and piperidyl; and where R: is a member selected from thegroup consisting of hydrogen, tetrahydrofurfuryl, lower alkyl, and lowerhydroxyalkyl.

12. A liquid petroleum composition consisting essentially of a liquidpetroleum lubricant hydrocarbon and a sufiicient amount of'a nitroamineto stabilize said hydrocarbon against metabolizing bacteria, saidnitroamine having the structural formula:

Rr-CHri -R where R is selected from the group consisting of lower alkyland hydrogen; where R, is a member selected from the group consisting ofN(R morpholino, piperidyl; and where R is a member selected from thegroup consisting of hydrogen, tetrahydrofurfuryl, lower alkyl and lowerhydroxyalkyl.

13. The composition of claim 12 wherein the composition contains fromabout p.p.m. to 2% by weight of the nitroamine.

14. The composition of claim 11 wherein the composition contains fromabout 100 p.p.m. to 2% by weight of the nitroamine.

15. The-composition of claim 11 wherein the composition is a cuttingoil.

16. The composition of claim 11 wherein the composition is a steamcylinder oil.

References Cited by the Examiner UNITED STATES PATENTS 2,419,506 4/47Senkus 260-583 2,465,958 3/49 Senkus 260-347.7 2,474,791 6/49 Senkus260-247 2,588,428 3/52 Stewart et a1. 167-22 2,812,332 11/57 Pennino167-33 2,913,414 11/59 Hodge 252-515 3,054,749 9/62 Bennett et a1252-8.55

FOREIGN PATENTS 107,419 5/39 Australia.

160,367 1/55 Australia.

421,189 3/47 Italy.

DANIEL E. WYMAN, Primary Examiner.

J ULIUS GREENWALD, Examiner.

11. AN AQUEOUS PETROLEUM EMULSION CONSISTING ESSENTIALLY OF AN AQUEOUS PETROLEUM LUBICANT HYDROCARBON EMULSION AND A SUFICIENT AMOUNT OF A NITROAMINE TO STABILIZE SAID HYDROCARBON AGAINST METABOLIZING BACTERIA, SAID NITROAMINE HAVING THE STRUCTURAL FORMULA: 